Stability properties of CO22

Abstract

The carbon dioxide molecular dication is investigated by multireference configuration interaction computations. Whereas the system is found to be unbound by De=-5.12 eV with respect to fragmentation into CO+(2 Sigma +)+O+(4Su), the ground-state potential energy surface of CO22+ enjoys a local minimum for a collinear symmetric configuration where the carbon nucleus is centred between the outer two oxygen nuclei (with internuclear separation RC-O=1.22 AA). Potential barriers larger than 1 eV render the corresponding electronic ground state 3 Sigma g- metastable against dissociative tunnelling. For the lowest seven excited states and system configurations restricted to linear symmetric geometries, potential energy curves are presented and compared with the experimental double ionization spectrum of CO2 in the Franck-Condon region.